EP0424523A1 - Composition pulverisable. - Google Patents

Composition pulverisable.

Info

Publication number
EP0424523A1
EP0424523A1 EP90908804A EP90908804A EP0424523A1 EP 0424523 A1 EP0424523 A1 EP 0424523A1 EP 90908804 A EP90908804 A EP 90908804A EP 90908804 A EP90908804 A EP 90908804A EP 0424523 A1 EP0424523 A1 EP 0424523A1
Authority
EP
European Patent Office
Prior art keywords
composition
water
polymer
pounds
clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90908804A
Other languages
German (de)
English (en)
Other versions
EP0424523B1 (fr
EP0424523A4 (en
Inventor
Thomas Nachtman
John Hull
Patrick O'shea
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Newastecon Inc
Original Assignee
Newastecon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Newastecon Inc filed Critical Newastecon Inc
Publication of EP0424523A1 publication Critical patent/EP0424523A1/fr
Publication of EP0424523A4 publication Critical patent/EP0424523A4/en
Application granted granted Critical
Publication of EP0424523B1 publication Critical patent/EP0424523B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/52—Mulches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/50—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle
    • B01F25/53—Circulation mixers, e.g. wherein at least part of the mixture is discharged from and reintroduced into a receptacle in which the mixture is discharged from and reintroduced into a receptacle through a recirculation tube, into which an additional component is introduced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B1/00—Dumping solid waste
    • B09B1/004—Covering of dumping sites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/021—Aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G2013/004—Liquid mulch
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/30—Landfill technologies aiming to mitigate methane emissions

Definitions

  • the present invention relates to a sprayable composition comprising a water-soluble polymer and clay, and to a method of spraying the composition for covering a material to be protected such as soil, refuse at a disposal site, or other material in a stockpile to form a protective water-resistant layer thereover.
  • U.S. Patent No. 3,763,072 to Krieger discloses a composition comprising an aqueous acrylic latex emulsion and sodium silicate for forming a crust on soil.
  • U.S. Patent No. 2,961,799 discloses a composition comprising a spray latex (styrene/butadiene) and clays for protecting soil from erosion.
  • composition preferably having the following advantages:
  • the present invention provides a sprayable composition for forming a cover layer over material to be protected such as, for example, (1) soil, (2) refuse at a disposal site, a sanitary landfill, or hazardous material landfill, or (3) a stockpile of material such as grain, salt or coal.
  • the composition can function as both a means of providing erosion control and/or a means for distributing seed and fertilizer over the soil.
  • the composition comprises: (a) a water soluble cellulosic polymer such as cellulosic polymer;
  • a carrier such as water for the polymer and clay, such that the composition, after spraying, becomes water-resistant, tough and flexible.
  • the present invention also provides a method of using the above described sprayable composition to form a cover layer over material, the method comprising:
  • a binder is preferably used in the composition to provide mass and toughness, a preferred binder being a fibrous mass such as shredded paper and/or wood.
  • Other materials are advantageously added to the composition such as one or more of the following additives: a surfactant, gypsum, a glue, or anti-foam agentborax, a dye, and an odor control agent.
  • the preferred composition contains the following ingredients in approximate pounds:
  • cover layers have been formed from a composition comprising: (a) a noniomic water soluble polymer of cellulose that is a hydroxyethyl ether of cellulose having a viscosity of about 100 to 5000 (Brookfield - #3 spindle) ;
  • the polymer is preferably a solvent soluble cellulosic polymer that preferably is a water-soluble cellulosic polymer having a viscosity of generally about 100 to 5,000 and preferably 500 to 2,000 Brookfield-#3 spindles) .
  • Solvent soluble cellulosic polymers are known in the art and available commercially, such as Cellobrand TM HEC water-soluble hydroxyethyl cellulose (trademark of the British Pilsylin Company - BP Chemicals, Ltd.) as set forth in their bulletin, Sept. 1982, 3625 162 7000, entitled Cellobond HEC hydroxyethyl cellulose, water-soluble polymer.
  • Natrosol TM hydroxyethyl cellulose (a trademark of Hercules Incorporated) as set forth, for instance, in their brochure dated 1980 entitled "Natrosol TM Hydroxyethyl Cellulose, a Nonionic Water Soluble Polymer” .
  • Natrosol HHR-250 (Hercules) as are other Natrosol 250 polymers as well as Natrosol 150 and 300 polymers.
  • Natrosol is produced in four levels of hydroxyethyl molar substitutes; 1.5, 1.8, 2.5 and 3.0, the polymers being designated 150, 180, 250 and 300, respectivel .
  • clay is preferably used with the polymer.
  • clay comprises a group of crystalline, finely divided earthy materials generally considered to be hydrates of alumina and silica, with iron oxide and magnesia as common minor components.
  • Bentonite clay is preferred, although kaolin, attapulgite and montmorillonite can be used.
  • Suitable clays are set forth in an IMV bulletin entitled MVITONE TM organoclays and clay products, Bentonite-Hectorite-Saponite-Sepcolite. IMV is a division of Gulf Resources and Chenuet Corp.
  • a suitable bentonite clay is sold by NL Bariod Supplies in a suitable mesh size of 200 mesh (60 to 325 mesh particles of a clay generally being very useful) .
  • shredded paper is a preferred fibrous material that is optionally, but advantageously, used.
  • U.S. Patent No. 3,812,615 discloses fibrous material for use in a foam for coating soil with a mulch, the patent being incorporated herein by reference.
  • the foamed material is made from an acrylic polymer, a polyepoxide, a wetting agent, a thickening material, water, and, of course, the fibrous material such as cellulose fibers, including wood pulps and other fiber sources such as old newspapers and cotton linters.
  • the fibrous material of the present invention includes such above-described fibers and also glass fibers, fibers from rice paper, straw and textile fibers.
  • the fibers are preferably short in length and thin in diameter, about 1/8 inch in diameter and 1/4 inch in length being about the maximum size for a sprayable composition.
  • the fibers are much shorter and thinner.
  • the fiber length is preferably less than about 1/2 inch and the average diameter less than about 1/4 inch.
  • a glue such as guar gum glue can be used to increase the adhesion properties of the composition.
  • a cellulosic polymer in addition to the cellulosic polymer such as Natrosol described above, can be used to increase the adhesion properties of the composition.
  • a cellulosic polymer in addition to the cellulosic polymer such as Natrosol described above
  • One such polymer is available from the Agualon Company of
  • gypsum is used to help provide stiffness and act as a hardener for faster setting up or curing.
  • the specific amount of gypsum which can be used may vary, but is generally at least 0.5% by weight and may be up to 10 - 15% by weight.
  • the amount of Natrosol polymer used will be approximately twice the amount of the Culminal polymer. Also, the amount of carrier or water used will be typically dictated by the desired spraying viscosity of the composition.
  • a surfactant especially the polymer, the clay, the carrier and, optionally, the fibrous material, adhesion agent, and gypsum
  • a surfactant especially the polymer, the clay, the carrier and, optionally, the fibrous material, adhesion agent, and gypsum
  • a surfactant especially the polymer, the clay, the carrier and, optionally, the fibrous material, adhesion agent, and gypsum
  • a preferable odor control agent is sold under the tradename CleanSense and is described in allowed U.S. Patent Application Serial No. 07/071,981, filed July 10, 1987, herein incorporated by reference.
  • materials such as fly ash, foundry sand, kiln dust, and bag house dust can be used to replace the fibrous material (preferably only up to about 50% by weight thereof) or even some or all of the clay (but preferably only 5 to 20 wt. % thereof, and usually no more than about 30 to 50 wt. % thereof) .
  • Useful surfactants include biodegradable surfactants such as non-ionic materials such as ethoxylated nonyl phenol (6 mole adduct) that is both water and oil 'soluble which is very easily used with the preferred carrier of water or even the carrier solvents such as oil, alcohols, methyl ethyl ketone and acetone.
  • biodegradable surfactants such as non-ionic materials such as ethoxylated nonyl phenol (6 mole adduct) that is both water and oil 'soluble which is very easily used with the preferred carrier of water or even the carrier solvents such as oil, alcohols, methyl ethyl ketone and acetone.
  • a suitable nonionic surfactant is N-60 (Texaco Chemical Co.) .
  • the optional materials can be used at about the same rate as the cellulosic polymer and the total weight of the additives (not including the fibrous material) is about like that of the clay (about 25 to 200 pounds per 4,000 pounds of carrier) .
  • the carrier used herein is preferably water, it has been found desirable in some instances to use a carrier other than water.
  • the composition is used as a covering material at a refuse site, the leachate which is collected at the site can be used as a carrier for the composition. It is believed that recycling the leachate into the site will enhance the natural bacterial action which acts to reduce the volume of the organic refuse, while also eliminating the need to transport leachate to a treatment plant.
  • a preferred composition has been found to include the following ingredients:
  • the amount of cellulosic fiber may vary up to 50%. Also the wood and paper blend may vary. In the example immediately above, the cellulosic fiber materials include approximately 30% wood and 70% paper. However, this may vary yp to 70% wood and 30% paper. The cellulosic fiber material may also have cardboard added and include for example, 20% cardboard, 40% wood, and 40% paper.
  • the composition will typically include from 5 - 30% by weight of seed, and approximately 10% by weight of fertilizer.
  • the cover layer of the invention usually, after spraying, has a thickness of about 1/16 or 1/8 inch up to 2 to 3 inches, although generally about 1/4 to 1 inch is preferred.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Fertilizers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Paper (AREA)
  • Pit Excavations, Shoring, Fill Or Stabilisation Of Slopes (AREA)
  • Paints Or Removers (AREA)
  • Protection Of Plants (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne une composition pulvérisable ainsi qu'un procédé de protection de matière à l'aide de ladite composition. Ladite composition comprend un polymère tel qu'une cellulose d'hydroxyéthyle, de l'argile, et de l'eau afin de ménager une couche de couverture, laquelle après pulvérisation est résistante, souple et hydrofuge. On peut utiliser d'autres matières telles que du papier déchiqueté et du gypse dans ladite couche de couverture. Ladite composition est efficace en tant que couche de couverture sur une matière telle que la terre, les ordures sur un site de décharge ou des grains dans un tas.
EP90908804A 1989-05-10 1990-05-10 Composition pulverisable Expired - Lifetime EP0424523B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US35059989A 1989-05-10 1989-05-10
US350599 1989-05-10
PCT/US1990/002691 WO1990013598A1 (fr) 1989-05-10 1990-05-10 Composition pulverisable

Publications (3)

Publication Number Publication Date
EP0424523A1 true EP0424523A1 (fr) 1991-05-02
EP0424523A4 EP0424523A4 (en) 1992-03-18
EP0424523B1 EP0424523B1 (fr) 1996-07-24

Family

ID=23377415

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90908804A Expired - Lifetime EP0424523B1 (fr) 1989-05-10 1990-05-10 Composition pulverisable

Country Status (11)

Country Link
EP (1) EP0424523B1 (fr)
JP (2) JP3062953B2 (fr)
AT (1) ATE140715T1 (fr)
AU (1) AU637103B2 (fr)
CA (1) CA2032501C (fr)
DE (1) DE69027903T2 (fr)
DK (1) DK0424523T3 (fr)
FI (1) FI910111A0 (fr)
GR (1) GR1000765B (fr)
IE (1) IE62623B1 (fr)
WO (1) WO1990013598A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994015886A1 (fr) * 1993-01-13 1994-07-21 Nachtman Thomas J Composition pulverisable et procede de production d'une couche de couverture protectrice et expansee d'exterieur
NL9401542A (nl) * 1994-09-22 1996-05-01 Inst Voor Agrotech Onderzoek Afdekmateriaal voor land- en tuinbouwgrond.
IL118787A (en) * 1996-07-04 2000-02-17 Israel State Method for applying plastic soil mulch
JP4524037B2 (ja) * 2000-12-20 2010-08-11 太陽工業株式会社 廃棄物処分場用の代替覆土材料、及びそれを用いた廃棄物を覆う層を形成する方法
JP4860789B2 (ja) * 2005-07-12 2012-01-25 株式会社モリタホールディングス 有機性廃棄物スラリーからの環境負荷ガスの排出を抑制する方法
JP4750624B2 (ja) * 2006-05-29 2011-08-17 カヤバ工業株式会社 ソレノイドにおけるチューブの製造装置及び製造方法
DE102009033833A1 (de) * 2009-04-26 2010-10-28 Terraelast Ag Verfahren und Sprühgerät zur Versiegelung einer Salzhalde
WO2012025564A1 (fr) 2010-08-27 2012-03-01 Universiteit Gent Barrières argileuses
WO2012151519A2 (fr) * 2011-05-04 2012-11-08 Lsc Environmental Products, Llc Compositions de revêtement de matériaux en vrac et procédés d'application associés
JP5964618B2 (ja) * 2012-03-13 2016-08-03 真哉 稲積 遮水性コーティング材および遮水性コーティング処理改良方法
CA2898558C (fr) * 2013-01-11 2020-02-18 Lsc Environmental Products, Llc Couverture de matiere volumineuse de reglage des odeurs
JP2014142312A (ja) * 2013-01-25 2014-08-07 Shimizu Corp 放射性物質の除去方法および塗料
CN112958580A (zh) * 2021-03-04 2021-06-15 荆州三迪建筑科技有限公司 生活垃圾无土覆盖方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802303A (en) * 1953-06-04 1957-08-13 Monsanto Chemicals Erosion control
EP0033997A1 (fr) * 1980-02-08 1981-08-19 Heidemaatschappij Beheer N.V. Procédé pour augmenter la résistance aux charges du sol
EP0052686A1 (fr) * 1980-11-26 1982-06-02 William J. Henning Compositions de revêtement isolantes et objets revêtus

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772893A (en) * 1972-06-07 1973-11-20 Dow Chemical Co Soil sealing method
JPS5144138B2 (fr) * 1972-08-21 1976-11-26
US3986365A (en) * 1975-02-20 1976-10-19 American Colloid Company Soil sealing method
JPS5842166B2 (ja) * 1975-09-17 1983-09-17 科研製薬株式会社 トフヨウフンマツノウヤクセイザイ
DE2851701A1 (de) * 1978-11-30 1980-06-19 Heinz Ing Grad Hoelter Granulat mit duenge- und/oder chemikalienzusaetzen und gleichzeitiger einfaerbung
US4232480A (en) * 1979-05-14 1980-11-11 Conwed Corporation Method and device for coloring bulk hydro mulch fibers
US4297810A (en) * 1980-03-03 1981-11-03 Hansford William B Sprayable hydromulch
US4414776A (en) * 1980-07-17 1983-11-15 Ball Harry J Fibrous web for planting seeds, method of using same, apparatus for producing same
US4369597A (en) * 1981-03-24 1983-01-25 Ronald B. Leep Pelletized mint mulch and method of making
US4787928A (en) * 1985-06-12 1988-11-29 Balassa Leslie L Hydrated fibrous mats

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802303A (en) * 1953-06-04 1957-08-13 Monsanto Chemicals Erosion control
EP0033997A1 (fr) * 1980-02-08 1981-08-19 Heidemaatschappij Beheer N.V. Procédé pour augmenter la résistance aux charges du sol
EP0052686A1 (fr) * 1980-11-26 1982-06-02 William J. Henning Compositions de revêtement isolantes et objets revêtus

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO9013598A1 *
WPI, FILE SUPPLIER, accession no. 77-31882Y [18], Derwent Publications Ltd, London, GB; & JP-B-58 042 166 (KAKEN KAGAKU KK) 17-09-1983 *

Also Published As

Publication number Publication date
GR900100348A (en) 1991-10-10
ATE140715T1 (de) 1996-08-15
IE62623B1 (en) 1995-02-22
EP0424523B1 (fr) 1996-07-24
AU637103B2 (en) 1993-05-20
DE69027903T2 (de) 1996-11-28
FI910111A0 (fi) 1991-01-09
JP3062953B2 (ja) 2000-07-12
JP3275093B2 (ja) 2002-04-15
JPH04500697A (ja) 1992-02-06
IE901688L (en) 1990-11-10
EP0424523A4 (en) 1992-03-18
DK0424523T3 (da) 1996-11-25
GR1000765B (el) 1992-12-30
CA2032501C (fr) 2001-07-17
WO1990013598A1 (fr) 1990-11-15
JP2000263010A (ja) 2000-09-26
DE69027903D1 (de) 1996-08-29
AU5677490A (en) 1990-11-29
CA2032501A1 (fr) 1990-11-11

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